IL30090A - Alkyl 1-carbamoyl-n-(substituted-carbamoyloxy)thioformimidates - Google Patents

Description

D'ORTO'tiOHDl 'Π AIKTL I-CARBAMOYL-J SUBSTITUTED-CARBAMOYLOXY) THIOFORMIMIDATES E. I. DU PONT DB NEMOURS AND COMPANY 30090/2 This invention relates to chemical pesticides and is more particularly directed to alkyl 1-carbamoyl-N-( subs f wherein ' 1 is alkyl of 1 through 4 carbon atoms or alkenyl of 5 through 4 carbon atoms; ·* Ra and R3 are the same or different and are hydrogen, alkyl of 1 through 4 carbon atoms, :. alkenyl of 3 carbon atoms, methoxy, or oyoloalkyl of 3 through 5 carbon atoms, with the proviso that R2 and R^ can be joined together and form an alkylene of 2 through 6 carbon atoms, and with the further proviso that 2 and R^ . ever total more than 7 carbon atoms and cannot both be cyoloalkyl or methoxy; - R4 is alkyl of 1 through 3 carbon atoms .or-allyl; and- , While there is an evergrowing number of chemical pesticides available to the public there is also a continuing need for pesticides which possess a desirable combination of physical properties, a desirable combination of pesticidal. activities/ or a desirable combination of pesticidal activity 30090/2 and good tolerance for plants and mammals. Thus, for example, many of the commercial pesticides are restricted in use because of toxicity to crop plants or to animals. Similarly, pesticides having outstanding combinations of properties' suc, as the hydroxamate carbamates described in U.S. Patent Specification Serial No. 3,576,834, nevertheless are unsuitable for use in some areas because, of low pesticidal activity or low safety margin for the host plant.

We have discovered that the compounds of formula (1) possess a surprisingly advantageous combination of physical properties, good activity towards serious economic pests, and high crop safety margins. ; Thus the compounds of formula (l) are useful in presenting the destructive effects of ticks, mites, insects and nematodes in a variety of applications, and are particularly useful in protecting plants from plant predaceous pests. They have demonstrated outstanding activity toward pests such as' the boll weevil, Anthonomus grandis and the Southern armyworm, Prodenla eridania, combined with good safety margins for their host plants. In addition to high levels . of' safety to seeds, fruits and foliage, the compounds of formula (l) have physical characteristics which permit them to be placed at the site of . nematode presence or activity readily and without disturbing plants already established. Additionally the compounds of formula (l) have demonstrated a good margin of safety to mammals and outstanding residual activity.

Description of the Invention As will be recognized by those skilled in the art, the compounds of formula (l) can exist in the form of either or both of the geometric syn and antl isomers.

The compounds of formula (l) which have shown the most desirable combination of properties and activity are those wherein R2 and R3 are both hydrogen or both methyl.

The most preferred compounds of formula (l) are methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformlmidate and methyl l-(dimethylcarbamoyl) -N- (methylcarbamoyloxy) thioformlmidate because of their outstanding pesticidal activity and safety margin on crops.

PREPARATION ' ·■·:■ Those compounds of formula (l) wherein R5 is hydrogen are prepared by reacting an appropriate 1-carbamoyl-N-hydroxy-thioformlmidate with a substituted- isocyanate in an inert solvent such as acetone. This reaction is illustrated by equation (A): A trace amount of a catalyst such as triethylamine or dibutyltin dilaurato can be used to" advantage in reaction (A) for some of the thioformimidates. ' ' ' 1 ■ Those compounds of formula (l) wherein ^ is methyl are prepared by reacting an appropriate thioformlmidate with sodium hydride in a solvent such as tetrahydrofuran and treating the resulting salt with a substituted carbamoyl chloride. This reaction is illustrated by equation (B) : The thioformimidate starting material for equations (A) and (B), which have both R2 and R3 as hydrogen, are prepared by reaction of l-carbamoylformhydroxamyl chloride with a mercaptan in the presence of a base. This reaction is illustrated in equation (C) : • - .7. ' " 0 NOH 0 NOH (C) HaN-C-Cr + RXSH Ν °Η > Hs -C-C^ CI SR1 ■ The l-carbamoylformhydroxamyl chloride can be prepared as described in Ber. 46, 2852 (1913).

An alternate procedure for the preparation of the thioformimidate starting materials is by .reaction of methoxycarbonylformhydroxamyl chloride with a mercaptan in the presence of a base and then reacting the product with an appropriate amine to form the desired 1-carbamoyl-N-hydroxythio ormimidate .

PESTS CONTROLLED Representative of the insects, ticks, mites and nematodes from which the compounds of formula (l) offer protection are the following: Aphids - Bean aphid - Aphis fabae Cabbage aphid - Brevicoryne brassicae Corn leaf aphid - Aphis maidis Corn root aphid - Anuraphis maidiradicls Cotton aphid - Aphis gossypii Green peach aphid - Myzus perslcae Potato aphid - Macrosiphum solanifolii Wooly apple aphid - Eriosoma lanigerum Armyworms - Fall armywonil - Laphygma frugiperda Southern armyworm - Prodenia eridania • Beetles - Asiatic garden beetle - Autoserica castanea j ■ Bean leaf beetle - Cerotoma trifurcata Cigarette beetle - Lasioderma serricorne Colorado potato beetle - Leptinotarsa decemlineata Japanese beetle - Popillia Japonica Mexican bean beetle - Epilachna varivestls Squash beetle - Epilachna borealis Sugarcane beetle - Euetheola regiceps White-fringed beetle - Graphognathus leucoloma Boll weevil - Anthonomus grandis Bollworm - Heliothis zea Borers European cornborer - Pyrausta nubilalis Peach tree borer - Sanninoidea exitiosa Squash vine borer - Melittia cucurbitae Sugarcane borer - Diatraea saccharalis Butterflies - Clouded sulphur - Colias philodice Imparted cabbageworm - Pieris rapae Caterpillars - Alfalfa caterpillar - Colias eurytheme Eastern tent caterpillar - Malacosoma americanum Curculio, plum - Conotrachelus nenuphar Earworm, corn - Heliothis zea (see bollworm) Plea beetles - Corn flea beetle - Chaetocnema pulicarla Potato flea beetle - Epitrix cucumeris Tobacco flea beetle - ' Epitrix hirtipennis Fleahopper, cotton - Psalius seriatus Flies - Black fly (citrus) - Aleurocanthus woglumi Hessian fly - Phytophaga destructor Horn fly -' Siphona irritans House fly - Musca domestica Stable fly - Stomoxys calcitrans, Fruit flies - Mediterranean fruit fly - Ceratitis capltata Mexican fruit fly - Anastrepha ludens Oriental fruit fly - Dacus dorsalis German cockroach - Blattella germariica Leaf rollers - Fruit tree leaf roller - Archips argyrospila Red-banded leaf roller - Argyrotaenia velutinana Leaf miners - Serpentine leaf miner - Liriomyza brassicae Leafhoppers - Beet leafhopper - Circullfer tenellus Potato leafhopper - Empoasca fabae Sugarcane leafhopper - Perkinslella saccharicida Leaf orm, cotton - Alabama arglllacea Maggot, seed-corn - Hylemya platura Mealybugs - Citrus mealybug- Pseudococcus citri Pineapple mealybug - Pseudococcus brevipes Mites - Citrus red mite - Paratetranychus citri Clover mite - Bryobia praetiosa European red mite - Panonychus ulmi Pacific mite - Tetranychus pacificus Two-spotted mite - Tetranychus urticae Mosquitoes - Common malaria mosquito - Anopheles quadrimaculatus Salt-marsh mosquito - Aedes sollicitans Southern house mosquito - Culex pipiens quinquefasciatus Moths - (Damage caused by immature forms called larvae) Clothes moth. - Tineola biselliella .

Codling moth - Carpocapsa pomonella European pine shoot moth - RhyacIonia buoliana Grape berry moth - Polychrosis viteana Gypsy moth - Porthetria dispar Melonworm - Diaphania hyalinata Oriental fruit moth - Grapholitha molesta Pickleworm - Diaphania nltidalis Nematodes - Awl nematode - Dollchodorus heterocephalus Banana nematode - Pratylenchus muslcola Bud and leaf nematodes - Aphelencholdes spp.

Burrowing nematode — Radopholus almilus Carrot root nematode - Heterodera carotae Coffee root-knot nematode - Meloidogyne exlgua Corn nematode - Pratylenchus zeae Dagger nematodes - Xlphinema spp.

Golden nematode - Heterodera rostochiensls Grass nematode - Angulna agrostls Lance nematodes - Hoplolalmus spp.

Lesion nematodes - Pratylenchus spp.

Northern root-knot nematode - Meloidogyne hapla Pea root nematode - Heterodera gottinglana Peanut root-knot nematode - Meloidogyne arenaria Pin nematodes - Paratylenchus spp.

Potato rot nematode - Ditylenchus destructor Reniform nematode - Rotylenchulus reniformus Rice nematode - Ditylenchus angustus Ring nematodes - Crlconemoides spp.

Smooth-headed lesion nematode - Pratylenchus brachyurus Southern root-knot nematode - Meloidogyne Incognita Soybean cyst nematode - Heterodera glycines Spiral nematodes - Helicotylenchus spp.

Stem and bulb nematode - Ditylenchus dipsaci Sting nematodes - Belonolaimus spp.

Stubby-root nematodes - Trichodorus spp.

Sugar beet nematode - Heterodera schachti.i Tobacco cyst nematode - Heterodera tabacum Tobacco stunt nematode - Tylenchorhynchus claytonl Pink bollworm - Pectinophora gossyplella Rootworms - Northern corn rootworm - Diabrotica longicornis Southern corn rootworm - Diabrotica undecimpunctata howard Western corn rootworm - Diabrotica vigifera Thrips - Onion thrips - Thrips tabaci Tobacco thrips - Frankliniella fusca Ticks - American dog tick - ermacentor variabilis Fowl tick - Argas persicus Rocky Mountain wood tick - Dermacentor andersoni Tobacco budworm - Heliothls virescens Weevils - Alfalfa weevil - Hypera postica Granary weevil - Sitophilus granarius Rice weevil - Sitophilus oryzae Sweetpotato weevil - Cylas formicarius elegantulus FORMULATIONS Compositions of this invention suitable for practic use as pesticides will include one or more compounds of formula (1) above either individually, in admixture with each other, or in admixture with other pesticides, and can include surface-active agents, solid or ^liquid diluents and other materials as desired to produce wettable powders, suspensions emulsifiable concentrates, dusts, solutions, granules, pelle or high-strength compositions.

Surfactants The surface-active agents or surfactants, as they are sometimes called, useful in formulating the compounds of this invention act as wetting, dispersing and emulsifying agents and assist dispersion of the active material in a spray. Additionally, the surfactants act as spreaders which aid in obtaining even coverage of the surfaces to be protected from insects and other pests. The surfactants can include such anionic, non-ionic and cationic agents as have been used heretofore in pesticidal compositions of similar type. A detailed list of such agents is found in "Detergents and Emulsi-fiers 1967 Annual," (John W. McCutcheon, Inc.).

Anionic and non-ionic surfactants are preferred in formulating compounds of this invention. Among the anionic surfactants, specific preferred ones are alkali and alkaline earth salts of alkylarylsulfonic acids such as dodecylbenzene-sulfonates and alkylnaphthalenesulfonates, dialkyl sodium sulfosuccinate esters, sodium lauryl sulfate, sodium N-methyl-N-oleoyltaurate, sodium dodecyldiphenyl ether dlsulfonate and the oleic acid ester of sodium isethionate. Among the non-ionic surfactants, preferred ones include octylphenyl polyethylene glycol ether, didecylphenyl polyethylene glycol ether, sorbitan fatty esters and their polyoxyethylene ethers, poly-oxyethylene ethers and thioethers of. long-chain alcohols and mercaptans as well as polyoxyethylene esters of fatty acids.

Preferred dispersants are alkali and alkaline earth salts of lignosulfonic acids, salts of polymerized alkylaryl-sulfonates which are sold under the "Daxad" and "Darvan" trademarks, as well as methylcellulose, polyvinyl alcohol and the like.

Surfactants can be used in compositions of this invention in amounts of up to 15# by weight based on the total weight of the resulting insecticidal composition.

Diluents The compositions of this invention can contain, with or without a surfactant, a finely divided solid diluent such as natural silicates, e.g., talc, sepiolite, pyrophyllite; clays, e.g., montraorillonite, kaolinite, attapulgite; dia-tomaceous earth, synthetic magnesium silicate, synthetic silicas, calcium silicate, calcium sulfate, calcium carbonate, calcium phosphate and flours derived from natural sources such as walnut shell, redwood, cottonseed, and the like. The finely divided solids can be used in the compositions of this invention at a concentration of 2 to 98$ by weight based on the total weight of the resulting pesticidal composition.

These finely divided solid diluents can be used in the preparation of water extendable concentrates containing from 75 to 98$ of a compound of this invention; dust-base concentrates of similar strength compounded for easy dilution with dusting diluents; wettable powders containing from 20 to 90$ of a compound of this invention; and dusts, usually ranging in active ingredient control from 2 to 2 $. Preferred finely divided solid formulations are high-strength compositions and powders containing 2 to 25$ of synthetic silica and 75 to 98 * active ingredients, with up to approximately 6$ of one or more surfactants optionally replacin some silica.

Solvents Organic liquids which are suitable for the preparatio of solutions, suspensions and emulsifiable concentrates of the compounds of this invention include alcohols, glycols, cello-solves, carbitols, ketones, esters, sulfoxides, amides, paraffinic hydrocarbons, aromatic hydrocarbons, and halogenate hydrocarbons. Ordinarily, solvent choice is dictated by the solubility of the active compound to be used and whether a suspension or solution is desired.

Preferred solutions are those containing 5 to 30$ active ingredient and 70 to 95$ solvent. Preferred solvents are dimethyl formamide and dimethylsulfoxide.

Suspension formulations comprise from 10 to 50$ of a compound of this invention dispersed in a non-solvent carrier. Dispersants and suspending agents can be present to improve the handling characteristics of such formulations. Suspension formulations are generally preferred if the solubility of the active ingredient in the liquid carrier is less than about 0.1$. In addition to non-solvent organic carriers, water can be used as a carrier for suspension concentrates of water- insoluble compounds of the invention.

For aerosol formulations low-boiling halogenated hydrocarbons are preferred as solvents and propellants, althou they can be partially replaced by low boiling hydrocarbons which act as propellants. Aerosol formulations ordinarily contain an organic or aqueous liquid in the range of 80 to 98$ by weight based on the total weight of the pesticidal composition.

Granules and Pellets Formulations in the form of granules and pellets are physically stable, particulate compositions containing a compound of formula (1) which adheres to or is distributed throug dimensions. In order to aid leaching of the active ingredient from the granule or pellet, a surfactant can be present.

Suitable carriers are of mineral or organic origin such as natural clays, some pyrophyllites, vermiculite and gypsum or ground nut shell and corncob. Suitable surfactants are anionic or non- ionic.

For the granule compositions of this invention, most suitable carriers are of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite heat expanded, granular, screened vermiculite; screened nut shell; or granular corncob. On such preformed granules, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight per cent of the total weight. The active agent is preferably applied in a volatile organic solvent when its solubility permits. Ordinarily, if an organic solvent is used, it is preferably selected from among methylene chloride, methyl cellosolve, dimethyl formamide and the like.

Preformed granules can also be treated with a melt of active ingredient if the active ingredients melting point is sufficiently below its decomposition temperature. When this means of application is used, the active ingredient in a very finely divided form is depositeid on the surface of the granules such as by tumbling in a mixer. The finely divided active agent can if desired contain minor amounts of diluents such as synthetic silicas, natural clays and surface active agents. After the active agent is distributed on the granules the granules are heated to above the melting point of the active agent preferably while tumbling is continued. The granules are then cooled and contain active ingredient within, as well The second type of carrier suitable for granules as well as pellets is initially in a powder form. Powdered kaol clays, hydrated attapulgite, bentonite clays such as sodium, calcium and magnesium bentonite or gypsum or plaster of Paris are blended with the active ingredient and the mixtures are then granulated or pelleted. Water soluble salts can be included in the compositions to aid in disintegration of the granules and pellets in the presence of moisture. Granules or pellets can be made containing 15 to 30 weight per cent of active ingredient, but more frequently concentration of 2 to 20 per cent is preferred for optimum distribution. Such granular compositions are most useful in a size range of 0.25 mm. to 1.4 mm.

The most preferred formulation for granules or pellets is 2 to 20 weight per cent active ingredient, 0 to 5 weight per cent surfactant and 75 to 98 per cent inert mineral carrier.

The above formulations can be prepared by methods generally used for pesticidal compositions of similar type. The solid compositions, with the exception of granules and pellets are prepared in a blending operation and will usually include passage through a grinder such as an attrition mill, a hammer mill or a fluid energy mill.

Solutions are prepared by stirring the combined ingredients; in some cases warming may speed solution and in others cooling or pressure may be required to prevent evaporation of the solvent. Aqueous and oil suspensions are prepared by mixing the insoluble active ingredient and other ingredient and ball milling or sand grinding the mixture to produce a concentrated slurry of very finely divided particles.

Modifiers Additional modifiers can be used to advantage in the compositions of this invention. Thus, although the compounds of formula (1) are quite stable under most conditions, the use of a desiccant, buffering agent or materials such as urea, which inactivate catalytic sites on diluent particles can prov desirable. Additives which will inhibit corrosion, reduce foa reduce caking and increase flocculation can also be used. In addition, bactericides, fungicides, bacteriostats and fungi-stats and other insecticides , acaracides and nematocides are often desirably present in the compositions of this invention in amounts of 0.025 to 10 parts by weight for each 1 part by weight of compound of formula (1). Suitable biologically active compound's are well known to those skilled in the art.

Of the biologically active compounds, those which ar insecticides and with which compounds of formula (1) are preferably combined include DDT; TDE; EPN; 3- (dimethoxyphos-phinyloxy)-N,N-dimethyl-cis-crotonamide ( "Azodrin"®); toxaphen "Strobane"® (chlorinated terpenes having a chlorine content of ca. 66$) ; and endosulfan.

Fungicides and fungistats with which compounds of formula (1) are preferably combined include pentachloronitro-benzene (PCNB); thiram; dodine; raaneb; methylmercury 2,3-di-hydroxypropyl mercaptide; methylmercury acetate; N-ethyl-mercury £-toluenesulfonanilide; l, -dichloro-2,5-dimethoxy-benzene; dimethyl ester of 2-carboxyamino-l-benzimidazole-carboxylic acid; N-trichloromethylthiotetrahydrophthalimide; N-trichloromethylthiophthalimide; sodium and calcium propionat and 3>3l-ethylene-bis(tetrahydro- ,6-dimethyl-2H-l,5,5-thia-diazine-2-thione) .

Bacteriostats and bacteriocides with which compounds of formula (l) are preferably combined include tribasic copper sulfate and streptomycin sulfate.

Specific combinations which are preferred and their area of exceptional utility include: (a) Methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate and methyl O-(methylcarbamyl) thioacetohydroxa- mate in ratios ranging from 1:4 to 4:1 for use on cotton plants. (b) Methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformlmi- date or methyl l-(dimethylcarbamoyl) -N-methylcarbamoyl- oxy) thioformimidate and l,4-dichloro-2, 5-dimethoxy- benzene (chldroneb) in ratios ranging from 1:6 to 6:1 for use on cotton seed. The chloroneb can be replaced in these combinations by one of the following compounds, their mixtures ith each other or their mixtures with chloroneb: pentachloronitrobenzene, captan; tetra- m methylthiurai disulfide; l-chloro-2-nitropropane; -ethoxy-3-trichloromethyl-l,2,4-thiadiazole; and p-dimethylaminobenzene-diazo sodium sulfonate. Such combinations are useful on seeds other than cotton including both vegetable and agronomic crops. (c) Methyl 1-carbamoyl-N- (methylcarbamoyloxy) thio ormimidate, chloroneb, and 2-carboxyamino-l-benzimidazole- carboxylic acid, dimethyl ester, in ratios ranging from 1:4:4 to 4:1:1, for use on cotton seed and other crop seed. <, (d) Methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate and DDT, in ratios ranging from 1:6 to 6:1 for use, the DDT can be replaced by one of the -following compounds, their mixtures with each other and their mixtures with DDT; endrinj carbarylj malathion; methyl parathion; parathion; "Guthion"® and toxaphene. (e) Methyl 1-carbamoyl-N- (methylcarbamoyloxy)thioformimi- date and 2-carboxyamino-l-benzimidazolecarboxylic acid, dimethyl ester, in ratios ranging from 1:3 to 3:1, for use on rice plants in seedbed, paddy o field for the control of insects. and disease. (f) Methyl 1-carbamoyl- - (dimethylcarbamoyloxy)thioformi- midate combined with EPN, carbaryl, "Guthion"®, malathion, methyl parathion or parathion, in ratios ranging from 1:4 to 4:1, for use on rice plants. (g) Methyl 1-carbamoyl- - (dimethylcarbamoyloxyJthioformi- midate combined with DDT, endrin, EPN, toxaphene, malathion, parathion, diazinon, "Guthion"®, carbaryl or methoxychlor in ratios ranging from 1:5 to 5:1* for- use on potato plants or cruciferous crops. The methyl 1-carbamoyl-N- (dimethylcarbamoyloxyJthioformi midate can be replaced in this combination by other compounds of formula (1) such as methyl 1-carbamoyl- N- (methylcarbamoyloxy)thioformiraidate . (h) Methyl 1-carbamoylrN- (methylcarbamoyloxy)thioformimi date combined with parathion, aldrin, diazinon or phorate, in ratios ranging from 1:3 to 3:1 for appli cation to soil prior to or during the planting of corn. The methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate can be replaced in this combination by other compounds of formula (1) such as methyl 1-carbamoyl-N- (dlmethylcarbamoyloxy Jthioformimidat (i) Methyl 1-carbamoyl-N- (methylcarbamoyloxy )thioforai date combined with DDT, methoxychlor, malathion, parathion, lead arsenate, "Guthion"®, carbaryl o dieldrin in ratios ranging from 1:4 to 4:1, for us on apples and other crops. (j) Methyl 1-carbamoyl-N- (dlmethylcarbamoyloxy)thiofor midate combined with DDT, carbaryl, EPN, toxaphene raethoxychlor or diazinon, in ratios ranging from 1:5 to 5:1 for use on. corn plants. (k) Methyl 1-carbamoyl-N- (methylcarbamoyloxy Jthioformi date combined with TDE, DDT, "Guthion"®, malathion diazinon, parathion or carbaryl, in ratios ranging from 1:6 to 6:1, for use on tobacco plants in seedbed or field. (1) Methyl 1-carbamoyl-N- (dimethylcarbamoyloxy )thiofor midate and chlordane, in ratios ranging from 1:8 t 8:1, for use on sugarcane seed pieces in the furro at the. time of planting. (m) Methyl 1-carbamoyl-N- (methylcarbamoyloxy )thioformi date combined with toxaphene, carbaryl, endrin, or "Guthion"®, in ratios ranging from 1:12 to 12:1, for use on sugarcane foliage. (n) Methyl 1-carbamoyl-N- (dimethylcarbamoyloxy )thio- formimidate combined with methoxychlor, carbaryl, malathion, DDT or toxaphene, in ratios rangin fro 1:4 to 4:1, for use on shade trees or forest lands (o) Methyl 1-carbamoyl-N-methylcarbamoyloxy) thio- formimidate combined with chlordane, DDT, diazinon or parathio'n, in ratios ranging from " 1:5 to 5'· 1 , for use in soil prior to or during planting of potatoes. : The use of pesticides, such as those mentioned above, in combination with the compounds of formula (l) sometimes offers an unexpected degree of plant protection. This is especially true when the compounds of formula (l) are combined with a fungicide and applied to the locus of a plant where both plant-parasitic nematodes and fungi are present. Thus, the combination of the compounds of formula (l) with pesticides such as l,4-dichloro-2, 5-dimethoxy benzene, methyl N-methyl-thlolcarbamate and 1, 2-dibromo-3-chloropropane are particularly ' preferred combinations.

APPLICATION In applying the compounds of formula (l) for pest control, the compound is of course applied in an amount sufficient to exert the desired pesticidal action. The amounts required to give pest control action however are governed by such variables as temperature, time of the year, moisture, type of application, pest species to be controlled and the like. Thus it is not possible to state any one- method or rate of application which would be generally satisfactory.

It is possible however to describe generally some of the ■ various methods and rates of application for certain areas of use and to which the compounds of formula (l) are best suited.

Thus, the compounds of formula (l) can be used to control plant-predacious insects and mites by distributing the chemical evenly over those plant surfaces which are infested or which are to be protected from subsequent infestation Due to the margin of safety for plants and animals characteristic of-the compounds of formula ( 1 ) such applications can be made without danger to the applicator or fear of damage to the plant when used as directed. Use rates for this type of application are in the range of 0.05 to kilograms of active ingredient per hectare. Rates of 0.1 to 17 kilograms per hectare are preferred and rates of 0.2 to 8 kilograms per hectare are most preferred for reasons of convenience and economy. This type of application may need to be repeated at intervals of 3 to 20 days. Such applications can be made with any of a variety of widely-available types of equipment ordinarily used for such applications.

Other effective methods of application include: a. To the seed of agricultural, horticultural and ornamental crops to protect the seed during storage and shipping prior to planting as well as to protect the seed and seedlings from attack by insects and mites after planting. The preferred rates for application to seed are in the range of 0.06 gram to j5 kilograms of the active compound of this invention per 100 kilograms of seed. The most preferred rates are in the range of 0.6 to 600 grams per 100 kilograms of seed. b. To soil in which plants are to be planted or are growing to protect seed and plants from attack by insects and mites. Such protection is against both soil insects attacking the roots and insects and mites attacking the above-ground parts of the plants . Preferred use rates are in the range of 0.1 to 60 kilograms of active ingredient per hectare treated. The most preferred rates are in the range of 0.3 to kilograms per hectare.

To the walls and floors of structures such as warehouses, stores, recreation buildings, factories, homes, poultry houses and barns to control insects, ticks and mites which could damage contents as well as attack or annoy people or domestic animals.! Applications to be repeated as needed.

To insects, ticks and mites that cause injury or annoyance, or carry disease to animals. The compounds of this invention can be applied to the animals to be protected by sprays, dusts or dips in such a way as to give a more or less uniform coating. Applications to be repeated as needed.

To land areas (including marsh or swamp) for the control of insects, ticks or mites causing injury or annoyance or disseminating disease to humans or animals. Preferred use rates are in the range of 0.01 to 10 kilograms of active compound of this invention per hectare 1 to 5 times. a year. The most preferred rates are in the range of .03 to > kilograms of active per hectare on the same schedule.

The compounds of formula ( 1 ) are also well suited to the control of plant-parasitic nematodes inhabiting soil in which the plants are planted or are to be planted. The physical characteristics of the compounds of formula (1 ) permit them to be placed readily at the site of nematode presence or activity without disturbing already established plants. The physical nature of the compounds of formula (1 ) permit their movement deep into undisturbed soil around plant roots, often ■ the site of nematode attack. The safety margin for plants make practical such application as well as application to soil being prepared for planting and application directly to seeds and growing plants at rates well above those required to control the nematodes.

Use rates for application to soil in which plants are growing are generally the same as those for application to soil being prepared for planting. Such rates range from about 0.15 to 225 kilograms of active ingredient per hectare of surface actually treated. Rates of 0.25 to 55 kilograms per hectare are most preferred for these uses for reasons of convenience and economy.

Other methods of applying the compounds of formula ( 1 ) to prevent the destructive effects of plant-parasitic nematodes include: spraying above-ground parts such as stems, leaves or buds in which nematodes are already present or where later attack is possible; dipping or soaking reproductive parts such as seeds, cane pieces or bulbs (which are already infested or are to be planted in infested soil) in a water suspension, solution or emulsion of the active ingredient; or immersing the root system or the entire plant of nursery stock or trans- plants in a water system to disinfest them or provide protectio against subsequent nematode invasion. The rates of active ingredient in the sprays or dips used as noted Just above are 12 grams to 4.8 kilograms per 100 liters of water.

Preferred rates are in the range of 30 grams to 1.2 kilograms per 100 liters.

In all of the applications discussed above, the distribution of the compounds of this invention may be simplified and made more accurate and economical by use of formulations as discussed previously.

The following examples further illustrate this invention. Parts and percentages referred to in the examples are by weight unless otherwise noted.

Example 1 A mixture of 12.5 parts of 1-carbamoyl ormhydroxamyl chloride, 79-2 parts of methanol and 10 parts of water is ( cooled to 5°C. and treated with 7 parts of methyl mercaptan. . To this mixture is then added gradually at -5 to 0°C, 8 parts of 50 aqueous sodium hydroxide which increases the pH to 8. The sodium chloride formed is filtered off and the filtrate concentrated until crystals form. The mixture is cooled well and filtered to give methyl 1-carbamoyl-N-hydroxythioformiini-date melting at 163-16 eC.

To a suspension of 4.5 parts of the methyl 1-carbamoyl-N-hydroxythioformimidate and 2.2 parts of methyl isocyanate in 20 parts of acetone is added a trace of Dabco, 1,4-diaza-bicyclo- S.2.2l7-octane. The reaction temperature rises to 55 °C. and then subsides and a white solid forms. After several hours at room temperature the mixture is filtered, giving methyl 1-carbamoyl- - (methylcarbamoylox )thioformimi-date melting at 162-164eC.

The compounds of Table I are prepared by the procedures of Example 1 using the mercaptans and isocyanates listed in place of the methyl mercaptan and methyl isocyanate of / Example 1.

TABLE Mercaptan Isocyanate ethyl mercaptan methyl isocyanate ethyl 1-carb idate allyl mercaptan methyl isocyanate allyl 1-carb idate but-2-enyl mercaptan ethyl isocyanate but-2-enyl 1 formimidat isopropyl mercaptan allyl isocyanate isopropyl 1- formimidat methyl mercaptan propargyl isocyanate methyl 1-car formimidat propyl mercaptan methyl isocyanate propyl 1-car formimidat allyl mercaptan allyl isocyanate allyl 1-carb formimidat isopropyl mercaptan methyl isocyanate isopropyl 1- formimidat butyl mercaptan methyl isocyanate butyl 1-carb idate sec. butyl mercaptan methyl isocyanate sec - butyl 1 formimidat Table I Mercaptan Isocyanate tert - butyl mercaptan methyl isocyanate tert - butyl formimidat methyl mercaptan ethyl isocyanate methyl idat butyl mercaptan ethyl isocyanate butyl l-carb idate methyl mercaptan isopropyl isocyanate methyl l-car formimidat butyl mercaptan isopropyl isocyanate butyl l-carb formimidat allyl mercaptan isopropyl isocyanate allyl l-carb formimidat allyl mercaptan ri-propyl isocyanate allyl l-carb formimi dat methyl mercaptan allyl isocyanate methyl l-car formimidat butyl mercaptan allyl isocyanate butyl l-carb formimidat allyl mercaptan propargyl isocyanate allyl l-carb formimidat Example 2 Methyl l-(dimethylcarbamoyl) -N-(methylcarbamoyloxy) - thloformimidate ' A solution of 206 parts of methylglyoxalate oxlme in 15OO parts of water is treated at 0 to -5°C. with 1 5 parts of chlorine in about 37 minutes. An oil of l-(methoxycarbonyl) -formhydroxamyl chloride is formed, which can be isolated by extraction with methylene chloride, evaporation of the methylene chloride and recrystallization from benzene, M.P. 63-65°C.

To the suspension of 1-(methoxycarbonyl)formhydroxamyl chloride in water as obtained above are added at 0 to -5" 105 parts of methyl mercaptan followed by 130 parts of 50$ aqueous sodium hydroxide mixed with 330 parts of water. The resulting two-phase reaction mass is then extracted with methylene chloride. Removal of the solvent under reduced pressure leaves the solid methyl 1-methoxycarbonyl-N-hydroxy-thioformimidate, which can be recrystallized from benzene, M.P. 63-64°C.

The crude methyl 1-methoxycarbonyl-N-hydroxythio-formimidate obtained above is dissolved in 2 0 parts of methanol and l80 parts of anhydrous dimethylamine dissolved in the solution below 30°C. This solution is allowed to stand at ambient temperature overnight. Removal of excess dimethylamine and the solvent under reduced pressure leaves 240 parts (74$) of methyl l-(dimethylcarbamoyl) -N-hydroxythio-formimidate.

To a suspension of 70 parts of methyl l-(dimethylcar moyl) -N-hydroxythioformimidate and 1/2 part of Dabco in 350 pa of acetone at 40° 0. is added slowly 27 parts of methyl isocyan The temperature of the reaction mixture rises to 58°C. After the temperature of the reaction mass has subsided to 25°C., th solvent is evaporated under reduced pressure, and the resultin one isomer of methyl 1- (dimethy1carbamoyl) -N- (methylcarbamoyloxy) -thioformimidate of M.P. 109-110°C. Recrystallization from water gives the other isomer of methyl l-(dimethyl-carbamoyl) -N- (methylcarbamoyloxy) -thioformlmldate of M.P. 101-103'C.

The compounds of Table II are prepared according to the procedures of Examples 1 and 2 using the mercaptans, amines/ and isocyanates listed in place of methyl mercaptan, dimethylamine and methyl isocyanate. one isomer of methyl 1- (dimethylcarbamoyl) -N- (methylcarbamoyl-oxy) -thioformimidate of M.P. 109-110°C. Recrystallization from water gives the other isomer of methyl 1- (dimethyl-carbamoyl) -N- (methylcarbamoyloxy) -thioformlmidate of M.P. 101-103°C.

The compounds of Table II are prepared according to the procedures of Examples 1 and 2 using the mercaptans, amines, and isocyanates listed in place of methyl mercaptan, dimethylamine and methyl isocyanate.

TABLE II Mercaptan Amine Isocyanate methyl mercaptan methylamine methyl isocyanate met b methyl mercaptan butylamine methyl isocyanate met b isopropyl mercaptan cyclopropylamine_ methyl isocyanate iso c allyl mercaptan N,0-dime hylhydroxyl- ethyl isocyanate all amine b butyl mercaptan allylamine ethyl isocyanate but o methyl mercaptan diallylamine allyl isocyanate met b ethyl mercaptan isopropylamine allyl isocyanate methyl mercaptan ethylamine propargyl isocyanate methyl mercaptan diethylaraine methyl isocyanate methyl mercaptan diisopropylamine methyl isocyanate met c ethyl mercaptan but-2-enylamine isopropyl isocyanate eth b Table II Contd.

Mercaptan Amine Isocyanate methyl mereaptan aziridine methyl isocyanate methyl mercaptan hexahydroaze ine methyl isocyanate methyl mercaptan pyrrolidine methyl isocyanate methyl mercaptan methylamine allyl isocyanate methyl mercaptan dimethylamine propargyl isocyanate methyl mercaptan allylamine propargyl isocyanate methyl mercaptan N,0-dimethyl- methyl isocyanate hydroxylamine methyl mercaptan N-methylethylamine allyl isocyanate met ( ethyl mercaptan piperidine allyl isocyanate eth c ethyl mercaptan piperidine butyl isocyanate eth c Table II Contd.

Merca tan Amine Isocyanate butyl mercaptan piperidine methyl isocyanate butyl carb butyl mercaptan piperidine butyl isocyanate butyl carb methyl mercaptan N-methylbutylamine methyl isocyanate methyl (meth methyl mercaptan N-methylallylamlne methyl isocyanate methyl (met meth lmercaptan cyclopentyl- methylisocyanate methyl amine K-( met m.p methylmercaptan cyclopropyl- methylisocyanate < methyl amine N-( met m.p methylmercaptan allylamine methy1isoc anate methyl carbara m.p , - 31 - Example 3 To a stirred suspension of 48 parts of 50# sodium hydride and mineral oil in 648 parts of tetrahydrofuran is added portion-wise over a one hour period 114 parts of methyl 1-carbamoyl-N-hydroxythioformimidate. The temperature is maintained at 20 - j$OeC. After subsidence of hydrogen evolution, 107.5 parts of dimethylcarbamoyl chloride is added dropwise at 15-25eC. Stirring is continued for one hour after the completion of addition. The inorganic solids are then removed by filtration and the methyl 1- carbamoyl-N-(dimethylcarbamoyloxy)thioformimidate is recovered by removal of the solvent under reduced pressure.

The compounds of Table III are prepared according to the procedures of Example 3 using the N-hydroxythioformi-midates and carbamoyl chlorides listed in place of methyl 1-carbamoyl-N-hydroxythioformimidate and dimethylcarbamoyl chloride .

TABLE III N-hydroxythloformimidate Carbamoyl Chloride methyl 1-carbamoyl-N-hydroxythio- N-allyl-N-methylcarbamoyl formimidate chloride methyl 1-carbamoyl-N-hydroxythio- N-methyl-N-propargylcar- formimidate bamoyl chloride methyl 1-carbamoyl-N-hydroxythio- N-methyl-N-propylcar- formimidate bamoyl chloride methyl 1-carbamoyl-N-hydroxythio- N-ethyl-N-methylcarbamoyl met formimldate chloride b methyl 1-methylcarbamoyl-N-hydroxy- dimethylcarbamoyl chloride thioformimidate methyl 1-dimethylcarbamoyl-N- dimethylcarbamoyl chloride met hydroxythloformimidate b methyl 1-cyclopentylcarbamoyl- dimethylcarbamoyl chloride N-hydroxythioformimldate propyl 1-carbamoyl-N-hydroxy- dimethylcarbamoyl chloride thloformimidate ethyl 1-carbamoyl-N-hydroxy- dimethylcarbamoyl chloride eth thioformimidate t butyl 1-carbamoyl-N-hydroxy- dimethylcarbamoyl chloride but thioformimidate t Table III Contd.

N-hydroxythioformimidate Carbamoyl Chloride methyl 1-piperdinocarbonyl-N-hy- dimethylcarbamoyl chloride dfoxy thioformimidate allyl 1-carbamoyl-N-hydroxy dimethylcarbamoyl chloride all thioformimidate t but-2-enyl 1-carbamoyl-N- dimethylcarbamoyl chloride but hydroxy thioformimidate A. Water-Soluble Powders It is possible to prepare wettable powders which become solutions rather than dispersions of active material in the spray tank. Then, as these solutions dry out on foliage the crystalline form may be restored. It is often advantageous to inhibit or control crystal growth during the drying step, so that the active ingredient remains in finely divided form. In other cases, larger crystals do not appear to diminish insecticidal activity.

Example 4 methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate 95$ synthetic fine silica $ A screened fraction of active material of less than 60 mesh is blended with fine silica to prevent agglomeration in storage. When added to water this crystalline form disperses satisfactorily without lumping and dissolves within a few minutes.

This formulation is dissolved in water and applied with conventional spray equipment at a. concentration of 120 grams - of formulation to 100 liters of water and a rate of , 2. 5 kilograms of active ingredient per hectare to bush snap beans being attacked by Mexican bean beetle (Epilachna varlvestls ) and the two-spotted mite (Tetranychus urti.cae) . The treated bean plants make rapid growth, have deep green leaves without the chewed areas characteristic of bean beetle attack, and produce a good yield of snap -beans . In an untreated area nearby, bean plants are stunted, have chlorotic and netted leaves and produce a poor crop.

Methyl 1- (dimethylcarbamoyl) -N- (methylcarbamoyloxy) - thiojformimidate formulated in the same manner as above and used in tobacco transplant water' at the rate of 15 milligrams V of active ingredient per plant, protects the tobacco plants from nematode attack resulting in rapid growth. and good tobacco yield.

Example 5 The water-soluble powder formulation of Example 4 is dissolved at the rate of '80 milligrams per liter of water and is used as transplant water in the amount of 235 milliliters for each tobacco plant being set in a field that is infested with the southern root-knot nematode (Meloldogyne incognita) , the stunt nematode (Tylenchorhynchus claytoni), the lesion nematode (Pratylenchus brachyurus) and tobacco wireworm (Conoderus vespertlnus) . The treated tobacco plants develop an extensive root system essentially free of root-knot, make rapid growth and yield well. Tobacco not so treated grows slowly and produces little marketable leaf.

Example 6 The formulation of Example 4 with methyl-l-(dimethyl-carbamoyl) -N- (methylcarbamoyloxy) thio^formimidate as the active ingredient is dispersed in water and used to treat sugarcane seed pieces being planted in muck soil in Florida so that the formulation is used at the rate of 3.5 kilograms of active ingredient per hectare1 of planted cane. The young plants are protected from the attack of the stunt nematode (Tylenchorhynchus martini) and make rapid growth compared to seedlings not protected in this manner.

Example 7 The formulation of Example 4 with methyl-1-(dimethyl-carbamoyl)-N-(methylcarbamoyloxy) thio^formimidate as the active ingredient is sprayed on an alfalfa field infested with the alfalfa stem nematode (Ditylenchus dlpsacl) at the rate of 1.25 kilograms of active ingredient per hectare In a volume of 60 liters per hectare. The treated alfalfa plants make rapid growth and produce deep green foliage while the plants in a nearby untreated area produce distorted growing tips and stems which are easily broken by the wind and have yellowish top growth.

Example 8 ■' The formulation of Example 4 with methyl-l-(dimethyl-carbamoyl) -N- (methylcarbamoyloxy) thio^formimidate as the active ingredient is sprayed around young, bearing citrus trees in Florida in a grove infested with the burrowing nematode (Radopholus similis). The material is applied at a rate of 4.5 to 9 kilograms of active Ingredient per hectare and washed into the soil with overhead irrigation. This application is repeated at three month intervals for a total of 3 applications. The trees are protected from burrowing nematodes, make rapid growth and bear a heavy crop of fruit. Citrus trees in a nearby grove not protected in this manner show a gradual decline in vigor and produce a light crop of fruit.

Example 9 methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate 75$ alkyl naphthalene sulfonic acid, Na salt 1 partially desulfonated sodium lignin sulfonate 10% synthetic fine silica l4# The above components are blended, micropulverized and then air-milled. When used in low volumes of water the active ingredient which falls to dissolve remains dispersed as a fine suspension. In larger volumes it all dissolves, but upon drying on foliage the crystal size is controlled by the lignin sulfonate present.

This formulation is dispersed in water and sprayed by means, of a tractor-mounted sprayer at a rate of about 1 . 5. kilograms of active ingredient in 50 liters of. water per hectare of cotton. Applications are made on a weekly schedule and finally on a five-day schedule during the latter part of the growing season. The treated cotton is protected from attackin boll weevil (Anthonomus grandls) and the bollworm complex including Hellothis zea and Hellothls ylrescens . The developing squares and bolls are retained by the plants, and a good yield of cotton fiber is obtained at the end of the season. In a nearby untreated field, the fruit set is markedly reduced by the several pests, and the yield, of cotton is greatly reduced.

Even much higher rates than those given above can be used with complete safety to the cotton plants. If infestations are very severe, better control can be obtained by combining the compound of this invention with one of the following: DDT, carbaryl, dimethyl parathion or "Azodrin" ®.

The same composition can be used to formulate : methyl 1-carbamoyl-N-(dimethylcarbamoyloxy) thioformimidate ethyl l-carbamoyl-N-(methylcarbamoyloxy) thioformimidate . , ethyl 1-carbamoyl-N- (dimethylcarbamoyloxy) thio ormimidate ' Example 10 The formulation of Example 9 is dispersed in water and sprayed at the rate of 10 kilograms of active ingredient in 200 dekaliters of water per hectare of a Zoysia lawn in Florida where the soil is heavily infested with sting nematode (Belonolaimus longicaudatus) and lance nematode (Hoplo-lalmus spp.). After spraying, the material is washed into the ground with the equivalent of about 1200 dekaliters of water per hectare. The grass in the treated area develops a deep root system and makes rapid growth, whereas grass in a similar but untreated area grows slowly and develops a Methyl l-(dimethylcarbamoyl) -N-(methylcarbamoyloxy) -thio^formimidate is formulated as in Example 9 and applied to another plot of Zoysia lavm in Florida similarly infested with nematodes. The formulation is applied in the same manner as above but at a rate of on y 2.5 kilograms of active ingredient in 200 dekaliters of water per hectare. The lawn thus treated exhibits similar beneficial effects to those described above.

Example 11 For the simultaneous control of the root knot nematode and soil fungi as represented by Pythium spp. and Rhizoctonia spp., the wettable powder formulation of Example 9 is applied in a spray which also contains 1,4-dichloro-2, 5-dimethoxybenzene . For this type of application, 2.4 kilograms active of the compound of this invention and 4.8 kilograms active of l,4-dichloro-2, 5-dimethoxybenzene is added to 100 liters of water. This mixture is applied as a soil spray by application to a 25 centimeter band over the row in which cotton is to be planted. The application rate in the row is 67.5 kilograms of total active (22.5 kilograms of the compound of this invention and.45 kilograms of l,4-dichloro-2, 5-dimethoxybenzene) per hectare of area actually treated. The soil is rotovated immediately thereafter to mix the chemicals thoroughly with the soil. Following this, cotton seed is planted in the treated band. The cotton seedlings which develop are protected against root knot nematode (Meloidogyne Incognita), the reniform nematode (Rotylenchulus reniformus) and the fungi Pythium spp. and Rhizoctonia spp. A healthy stand of cotton plants is obtained and at harvest time, a high yield of cotton. Where no treatment is applied, the stand is poor, growth is slow and lint yield is reduced.

Methyl l-(dimethylcarbamoyl) -N-(methylcarbamoyloxy) -thio^ ormimidate is formulated as in Example 9 and is applied in a spray along with l,4-dichloro-2, 5-dimethoxybenzene to soil prior to planting with cotton seed in the manner described above. The application rate in the row is 6 kilograms of the compound of this invention and 45 kilograms of l,4-dichloro-2, 5-dimethoxybenzene per hectare of area actually treated. The soil is rotovated immediately thereafter to mix the chemicals thoroughly with the soil. Cotton seed is planted in the treated band. Cotton seedlings are protected from root-knot and reniform nematodes as well as the attack of Pythlum and Rhlzoctonla fungi. The plants develop an extensive deep root system and make rapid growth.

Even much higher use rates than those given above can be employed with complete safety to the cotton plants.

Example 12 The formulation of Example 9 is added to water in an amount to give 45 grams of active ingredient per 100 liters of spray. This solution-dispersion is sprayed on apple trees to the point of run-off by means of a high pressure hydraulic sprayer. Sprays on a weekly schedule provide control of green apple aphid, codling moth, plum curculio and redbanded leaf roller. One or more of the following insecticides in effective amounts can be added to the spray when a longer interval between applications is desired or it. is needed to control other especially difficult-to-control pests: DDT, methoxychlor, malathion, lead-arsenate, "Guthion" ®, or carbaryl.

Example 15 The wettable powder formulation of Example 9 is dispersed in water and sprayed by means of a conventional sprayer over a lawn and adjacent vegetation infested with the American dog tick (Dermacentor variabilis).. An amount of the formulation is used to give 6 kilograms of 800 liters of water per hectare of area sprayed which effectively controls the pest.

Example 1 The formulation of Example 9 is dispersed in water, and drenched on the soil over the root zone of boxwood plants infected with the spiral nematode (Helicotylenchus buxophilus) at a rate of 5. 5 kilograms of act.ive agent per hectare of area treated using enough water to wash the active agent down about the plant roots. Substantially all spiral nematodes are controlled by this treatment, allowing the boxwood plant to develop in a normal manner. Similarly infested boxwood plants which are left untreated grow poorly and finally die.

Example 15 n-propyl^l-carbamoyl-N-(methylcarbamoyloxy) thioformimidate 0$ cTioctylsodium sulfosuccinate . 1 . low viscosity methylcellulose 2.0 dlatomaceous silica 7.

The above composition is blended and micropulverized until substantially all particles are less than 50 microns.

The resulting wettable powder can be added to water and sprayed, or extended with heavy diluents to form a dust.

For example : composition above 20$ ground pyrophylllte 80$ These components are blended in a ribbon or cone blendor to form a 10$ active dust.

The 10$ active dust is applied in thorough coverage by means of a hand crank-operated duster to both the upper and lower surfaces of the foliage of rose bushes still wet with morning dew. Infesting aphids such as the potato aphid (Macroslphum euphorblae) and the rose aphid (Macroslphum rosae as well as feeding-adults of the Japanese beetle (Popillia japonica) are controlled by this application. The above dust can be formulated to contain $ "Manzate"®in the finished product to also give control of the disease called black spot (Dlplocarpon rosae) , which frequently affects roses. Roses treated with this combination make good growth, possess shiny deep-colored foliage and produce numerous buds. Adjacent untreated bushes exhibit poor growth, drop numerous yellowed leaves and fail to produce the expected crop of bloom Example 16 A wettable powder formulation of Example 15 is prepared using methyl 1-(dimethylcarbamoyl) -N-(methylcarbamoyloxy) thio# formlmidate as the active ingredient. This formulation is use to treat farm land in Florida infested with the stubby-root nematode (Trlchodorus chrlstiei) and the lesion nematode (Pratylenchus zeae) . The material is applied as a spray at the rate of 2.25 to 4.5 kilograms of active ingredient per hectare of land and thoroughly mixed with the soil by disking. Sweet cprn planted in this treated field develops a deep and extensive root system, makes rapid growth and yields a heavy crop of marketable ears. Corn in a nearby untreated field grows slowly and produces a low yield.

Example 17 The wettable powder formulation of Example 16 is sprayed around young, bearing apple trees in Holland that are infested with lesion nematodes (Pratylenchus spp.)."' Application is made by spraying within the drip line of the trees at the rate of 2.25 to 4.5 kilograms of active ingredien per hectare of area actually treated. The trees make rapid growth as a result of the treatment in contrast to nearby untreated trees.

Example 18 Chickens are temporarily removed from a poultry house and surrounding areas which are heavily infested with the fowl tick (Argas perslcus) . The house and areas are thoroughly dusted with a 10$ dust formulated from the dust concentrate of Example 15. The infestation is controlled and the poultry returned to the house soon assumes a healthy appearance and resumes egg-laying at the normal; level.

Example 19 The wettable powder formulation of Example 15 is applied in a spray covering a 25 centimeter band over the open furrow as cotton seed are being planted. For this type of application 2.5 kilograms of active ingredient per , 000 meters of row is applied in 75 liters of water. The active ingredient of this invention moves by means of systemic action from the soil into the cotton seedlings to render them toxic to certain sucking insects. Infestations of aphids, thrips species and plant-sucking bugs are thereby controlled. Plants in the treated area grow rapidly and produce full green foliage. Plants in a similar but untreated area grow slowly and have thickened silvery leaves, the latter due to thrips injury.

Much higher use rates for the pesticidal formulation than those given above can be employed with complete safety . to the cotton plants.

Example 20 isopropyl 1- carbamoyl-N- (methylcarbamoyloxy)thio- formimidate 25.0 alkyl naphthalene sulfonic acid, Na salt 0.5% sodium- N-methyl-N-palmitoyl taurate 2.0% attapulgite clay 7 .5%.

The above components are blended and mikropulverized until substantially all particles are below 50 microns.

This formulation is dispersed in water at the rate of 480 grams of the above formulation in 10 liters of water and used to spray to the point of run-off the walls, floors, stalls, and pens of barns infested with the house fly, Musca domestica. Control of this troublesome pest results.

The other compounds of formula (1) can be similarl formulated to give a satisfactory wettable powder.

C. Dust Base Example 21 methyl 1-carbamoyl-N- (dlmethylcarbamoyloxy )thioformimidate Micaceous talc The above components are blended and mikropulverized until substantially all particles are less than 100 mesh. The resulting free flowing powder can be diluted with the same or other extenders to produce 2-2 active dusts by simple blending.

The above dust concentrate is. blended with talc to/ give a 5% active finished dust. When this dust is applied i thorough coverage by means of a crank-ope ated duster to potato plants infested with the potato aphid, Macrosiphum euphorbiae, and the green peach aphid, Myzus perslcae, excellent control of the infestation results, ^ien other insects such as Colorado potato beetle, flea beetles and leafhoppers are present, addition of one of the following products to the pesticidal formulation can be made to improv D. Water-Miscible Solution Example 22 A homogeneous solution is prepared by simple mixing of the above components. When added to water, there is a temporary milkiness produced by separation of the active followed by total solution if the final active concentration is low.

In a low volume concentration spray, some active may remain undissolved but coarse crystal growth is inhibited by the presence of the surfactant.

The above emulsifiable concentrate is diluted with water and sprayed at the rate of 17 kilograms per hectare of active ingredient in 115 dekaliters of water on a field infested with the sugar beet nematode (Heterodera schachtii) and the chemical is worked into the soil to a depth of 6 inche. Sugar beets subsequently grown in this field develop normally and are substantially free from infestation by nematodes. In a similarly infested but untreated area in the same field, beets are distorted and yields reduced.

Example 23 The water-miscible formulation of Example 22 is dispersed in water and used to treat cotton seed at the rate of 750 grams of the active ingredient per 100 kilograms of seed. Seed treated in this manner produce seedlings which are protected from attacking insects and control infestations of the cotton aphid (Aphis gossypii ), the serpentine leaf miner (Liriomyza brassicae ) and tobacco thrips (Frankliniella fusca) for a period up to 3 weeks or more after planting.

Cotton survival is also improved if chloroneb is applied to . the cotton seed along with the above concentrate .at the rate of 375 grams of active per 100 kilograms of seed. And cotton survival is further improved if, as a third component of the treating preparation, "Ceresan"® L is applied in an amount to provide 200 milliliters of "Ceresan"® L per 100 kilograms of cotton seed. The chloroneb in this mixture can be replaced by one or more of the following: pentachloronitrobenzene; captan; tetramethyl-thiuram disulfide; l-chloro-2-nitro-propane; 5-ethoxy-2-trichloromethyl-l, 2, 4-thiad¾zole; and p_-dimethylaminobenzene-diazo sodium sulfonate.

Example 2 The water-miscible composition of Example 22 is dispersed in water and applied as a wetting spray by means of a hydraulic sprayer at a rate of 1 kilogram active per hectare to cabbage plants infested with the imported cabbageworm, Pieris rapae, and the cabbage looper, Trlchoplusia ni.

Treated plants are protected from the worm feeding and produce firm heads with full wrapper leaves. Plants in a nearby un- treated row are riddled by the worm feeding and produce mostly unmarketable heads .

Example 25 The water-miscible formulation of Example 22 is added to water at the rate of 30 grams per 100 liters. The roots and lower stem of woody nursery stock known to be infested with the lance nematode (Hoplolaimus coronatus ) are dipped in this solution for three minutes. When stock so treated is planted it grows well and is of good appearance. Similar stock which is not treated grows poorly, is of poor appearance, and, in many instances, does not survive.

Example 26 compound per 100 liters. Tobacco plants infested with tobacco budworm (Heliothis ylrescens) and hornworms (Msnduca s p. ) are sprayed with the above material to run-off, Excellent Icon trol is obtained by applications made on a 10-day interval.

Example 27 al yl 1-carbamoyl-N- (nethylcarbattoyloxy )thioformifflidate 25$ dimethylsulfoxide 75» A clear solution is formed when these components are mixed.

When used at the rate of 0.5 pounds active per 100 gallon water a clear solution results.

This composition is diluted,with water to give a final concentration of 0.2# active. House flies, Musca domestica, and other flies such as stable flies, Musca autumrialis, are controlled in farm buildings, barns, and outdoor locations such as pens and corrals by spraying with this preparation as a space spray using a mist blower.

I E. Oil Suspension Example 28 ethyl l-carbamoyl-N-(ethylcarbamoyloxy)thioformimidate 50* polyethylene oxide lauryl ether o% low viscosity white oil (Liteteck oil) 62# The above components are mixed and sand milled until the active is substantially all below 10 microns. The resulting suspension can be emulsified in water and sprayed or can be diluted with a nonphytotoxic paraffin oil and sprayed. For ultra low volume use the concentrate can be sprayed as it is .

This formulation when diluted with water to give 2.2 kilograms of active ingredient per 2jJ0 liters is sprayed at the rate of 250 liters per hectare on corn directinc the spray toward the silks of developing ears. When applied in such a the silkin eriod at an interval of 1 to 2 da s, Example 29 The oil suspension of Example 28 is diluted with a paraffin oil to give 2.4 kilograms active per 100 liters.

This is applied as a spray by means of airplane at the rate of 9A liters per hectare to marshlands and swampy areas serving as the breeding grounds for various species of mosquitoes. Control of the developing mosquito larva is obtained with this application.

F. Aerosol Formulation Example 30 methyl 1-carbamoyl-N- (raethylcarbamoyloxy )thioformimidate equal wt. mixture of rtFreon ll,,(!>and "Freon 12"® 98# The above mixture is cold packed In an aerosol can for flying insect control.

The above aerosol is discharged at the rate of l40 to 350 grams of active ingredient per 1,000 cubic meters of. space in a greenhouse in which carnations are growing. Plant injury is prevented by attaching a wand to the aerosol container and discharging the material above the plants. This application controls aphids such as the green peach aphid, Myzus perslcae, and the leaf-curl plum aphid, Aphis heli-chrysi, infestin the carnation plants..

G. Aqueous Dispersion Example 31 allyl 1-carbamoyl-N- (dimethylcarbamoyloxy )thioformimidate 5 Carbopol 93 (a polycarboxylic hydrocarbon polymer) 0.4 $ aqueous NaOH 1.00 NaaHPO* 1.00 "Elvanol"® 51-05 (polyvinyl alcohol) , 1.00 sulfated tallow defoamer 0.1 water 6l.5# The Carbopol and Elvanol are first blended dry with the active to avoid lumping. The NaOH and Na2HPC- are predissolved in. the water. The solids and antifoam are then added and the mix sand ground until the active is substantially all below 10 microns .

The aqueous dispersion is diluted with water and sprayed on selected plots in a strawberry field known to be heavily infested with the bud and leaf nematode (Aphelenchoidea besseyi) . The spray solution contains 120 grams active of the composition of this invention per 100 liters of water.

The volume of application is such as to provide 2.2 kilograms of the active ingredient per hectare of plot area. All above-ground parts are thoroughly wetted. The strawberry plants in the sprayed plots grow well and give a good yield. In the un-sprayed portions of the field the plants are yellow, grow slowly and produce a poor yield.

H. Granules Example 32 methyl 1-carbamoyl- - (methylcarbamoyloxy)thioformimidate dimethylformamide # granular attapulgite with particles ranging from 0.25 to 0.6 mm. 96 The active ingredient is first dissolved in the dimethylformamide at an elevated temperature and is then sprayed upon the attapulgite while it is being tumbled. Due to low volatility the solvent remains in the granule for an extended time but does slowly evaporate.

The other compounds of formula (1) can be formulated as granules in the same manner.

The above granular formulation, containing methyl 1-carbamoyl-N- (dimethylcarbamoxyloxy )thioformimidate as the active component, is applied in the planting furrows of potatoes at the rate of 3 kilograms of active ingredient per 10,000 meters of row. Certain soil-infesting pests of potatoes such as white- fringed beetle larvae, mole crickets and wireworm larvae are greatly reduced in numbers. The potato plants are protected from infestations of potato aphid, Macrosiphum euphorbiae, and green peach aphid, Myzus persicae, due to the systemic movement of the compound of this invention from the soil up into the potato foliage.

Example 33 methyl 1-carbamoyl-N- (dimethylcarbamoyloxy )thioformidiate 5# polyethylene oxide trimethylnonyl ether 5# granular vermiculite 89 synthetic fine silica 1 The active and fine silica are first mixed and mikropulverlzed. This dust is then mixed briefly with the granular vermiculite and sprayed with the liquid surfactant.

Other compounds of formula (1) can be formulated as granules in the same manner.

The above granular formulation, containin methyl 1-carbamoyl-N- (methylcarbamoyloxy Jthioformimidate as the active ingredient, is applied in the furrow with cotton seed at the time of planting at the rate of 2.5 kilograms of the active ingredient per 10,000 meters of row. The resulting seedlings are protected from attacking insects due to the systemic movement of the compound of this invention from the soil into the seedling. Infestations of the cotton aphid, Aphis gossypii, various thrips species, and the serpentine leaf miner, Example 34 The granular formulation of. Example 33 containing methyl 1-carbamoylrN- (methylcarbamoyloxy)thioformimidate as the active ingredient is applied as a sidedress treatment to cotton plants at the start of squaring (fruiting) at the rate of 7.5 kilograms of active ingredient per 10,000 meters of row. Adult boll weevils, Anthonomus grandis, emerging from hibernation and feeding on the foliage and young fruit buds are controlled due to the systemic movement of the compound of this invention from the soil up into the plant parts.

Example 5 The granular formulation of Example 33 containing methyl 1-carbamoyl-N- (methylcarbamoyloxy)thioformimidate as the active ingredient is applied in the furrow with corn seed at the time of planting at the rate of 2.5 kilograms of the active ingredient per 10,000 meters of row. Larvae of the northern corn rootworm, Diabrotica longicornis, and the western corn rootworm, Diabrotica virgifera, hatching from eggs deposited by adult females in the soil the previous Fall and attack-ing the corn roots are controlled. The corn makes rapid growth, develops a deep root system that prevents the plants from lodging during windy periods and produces a good yield. Plants in a nearby area left untreated develop a shallow root system that causes a goodly percentage of lodged plants and the yield is greatly reduced.

Example 36 The granular product of Example 33 is applied to soil infested with plant-pathogenic nematodes at a rate of kilograms active agent per hectare using a conventional fertilizer spreader. The active agent is then worked into the soil by disking. This treatment gives substantially complete control of a high population of the sting nematode (Belonolaim longicaudatus ) as shown by a nematode count 15 days after trea ment. In a similar area that remains untreated, the populatio of the sting nematode continues at a damaging level.

Example 37 allyl 1-carbamoyl-N- (methylcarbamoyloxy )thioformimidate 10 gypsum plus ammonium sulfate 90 The above components are blended and granulated by the procedu described in U.S. Patent No. 3, 168, 37, to give rapidly disintegrated granules ranging in particle size from 0.25 to 1 mm.

The other compounds of formula ( 1 ) can be substitute for the active Ingredient shown above and the active concentra tion can range from 2- 0$ without loss of physical properties.

The above granular formulation is applied at the rate of 20 kilograms of active ingredient per hectare using a conventional fertilizer spreader. The material is then worked into the soil by disking. Tobacco grown subsequently in this field is substantially free from infestation by the lesion nematode (Pratylenchus brachyurus ) and the southern root knot nematode (Meloidogyne incognita). Soil-infesting insects such as mole crickets and wireworm larvae that damage tobacco are also controlled. The tobacco plants in this field make rapid growth and yield well while tobacco on a similar but untreated area grows slowly and produces little marketable leaf.

Methyl l-(dimethylcarbamoyl) -N- (methylcarbamoyloxy) -thiolformimidate is formulated as a granule in the same manner ■ ■ Application of this formulation to a field at the rate of 5 spreader, is followed by disking into the soil. Tobacco grown in this field is protected from attack by the lesion nematode and southern root-knot nematode. As a consequence, the plants make rapid growth and yield well.

Example 38 The formulation of Example 37 with methyl l-(dl-methylcarbamoyl) -N-(m thylcarbamoyloxy) thiojformimidate as the active component is applied at the rate of 5 kilograms of active ingredient per hectare with a fertilizer spreader to a field infested with the soybean cyst nematode (Hetero-dera glycines) . The granules are thoroughly mixed into the soil by disking. Soybeans grown in this field produce vigorous green plants that yield well. Plants grown in a nearby untreated field are small, have yellowish foliage and yield poorly.

Example 39 The formulation of Example 37 with methyl l-(di-methylcarbamoyl) -N-(methylcarbamoyloxy) thiojtf*ormimidate as the active component is applied at the rate of 5 to 12. 5 kilograms of active ingredient per 10,000. meters of row in a potato field infested with the golden nematode (Hecterodera rostochiensis) . Application is made by dribbling the granules in the open furrow prior to placing the potato seed pieces. The potato plants in this field produce dark-green vigorous plants and a high yield of potatoes at the end of the season. A nearby untreated field produces small plants that yield poorly at the end of the season.

Example 40 The formulation of Example 37 with methyl l-(dl-methylcarbamoyl) -N-(methylcarbamoyloxy) thio/formimidate as the active component is used to treat a field in which grape cuttings are to be set and which is infested with the dagger nematode (Xiphlnema index) . Application is at the rate of 4 to 8 kilograms of active ingredient per hectare with a fertilizer spreader followed by disking into the soil. Grape vines grown in this field are protected from the dagger nematode and the virus that it transmits which causes a condition known as "fanleaf".

Example 41 The formulation of Example 37 with methyl l-(di-methy1carbamoyl) -N-(methylcarbamoyloxy) thio^formimidate as the active component is used to treat a field in Hawaii infested with the reniform nematode (Retylenchulus reniformls) and the pin nematode (Paratylenchus minutus) . Application is at the rate of 3 to 8 kilograms of active ingredient per hectare with a fertilizer spreader followed by disking into the soil. Pineapple plants grown in this field develop a deep extensive root system and make good growth. Plants in a nearby untreated field are small and grow slowly due to a poor root system.

Example 42 The formulation of Example 37 with methyl l-(di-methylcarbamoyl)-N-(methylcarbam0yloxy)thio formlmidate as the active component is used to treat celery in Connecticut in land infested with the pin nematode (Paratylenchus hama-tus) . After the small plants are set in the field, the granules are applied as a side-dressing on both sides of the row in the amount of 5 to 12.5 kilograms of active ingredient per 10,000 meters of row. Overhead irrigation is applied to aid in the break-down of the granules and to wash the active ingredient into the soil. The celery- plants in this field grow rapidly and develop a deep green color while plants in a nearby untreated field are stunted and chlorotic.

Example 43 The formulation of Example 37 with methyl 1- (dimethylcarbamoyl) -N-(methylcarbamoyloxy) thio^formimidate date as the active component is applied around young coconut-palm trees infested with the coconutpalm nematode (Rhadina-phelenchus cocophilus) . The ma'terial is applied within the drip-line of the trees at a rate of 5 to 8 kilograms of active ingredient per hectare of area actually treated. The granules are then lightly worked into the soil. Trees so treated continue to grow and bear while nearby untreated trees grow slowly and eventually die.

Example 44 ·. ',·■ The formulation of Example 37 with methyl 1- (dimethylcarbamoyl)-N-(methylcarbamoyloxy) thio^formimidate as the active component is used to treat young tea plants in Ceylon infested with lesion nematodes (Pratylenchus spp.). The granules are dribbled along each side of the row of young plants so that 5 to 12.5 kilograms of active ingredient is applied per 10,000 meters of row. The granules are then worked lightly into the soil. Applications are repeated at six-month intervals. Plants treated in this manner grow rapidly and yield early compared to untreated plants.

■Example 4 The formulation of Example 37 with methyl 1-(dimethylcarbamoyl) -N-(methylcarbamoyloxy) thio^formimidate as the active component is applied around young banana plants in Honduras infested with burrowing nematodes (Radopholus similis) and lesion nematodes (Pratylenchus spp.). The granules are distributed around the young plants to cover the root area at a rate of 2.25 to 5.6 kilograms of active ingredient per hectare of area actually treated. .The granules are worked lightly into the soil and are dissolved by the soil moisture. The application is repeated after about 3 months to give complete control of nematode injury. Plants treated in this manner grow rapidly and bear heavily while untreated plants grow slowly and bear little fruit.

Example 46 Methyl 1-(dimethylcarbamoyl) -N-(methylcarbamoyl-oxy) thio^formimidate is dissolved in water used as the transplant water fo strawberry plants so that 20 milligrams of the compound is applied with each plant. The material is translocated within the. plant to protect the developing young leaves from the bud and leaf nematode (Aphelenchoides besseyl) which causes a condition known as summer crimp. Protected plants make rapid growth and high yield while nearby unprotected plants exhibit small deformed leaves and produce little or no fruit.

Example γ- Methyl l-(dimethylcarbamoyl) -N-methylcarbamoyl-oxy) thio formimidate is slurried in water and used to treat cucumber seed at the rate of 1.25 grams of chemical to 1 kilogram of seed. Seed treated in this manner produce seedlings that are/protected from attack by southern root-knot nematode (Meloidogyne incognita) for a period up to three weeks after planting. Periods of longer protection rapid growth and produce early and heavy yields of marketable cucumbers. ■ The compound of this invention is very safe to the seed and can be used at rates as high or higher than 10 grams of chemical to 1 kilogram of seed without causing any injury whatsoever to the seedlings. A seed treatment such as thiram is used in conjunction with the compound of this invention to protect the seed from fungal attack after planting.

Example 48 Methyl l-(dimethylcarbamoyl) -N- (methylcarbamoyl-oxy) thio formimidate is dissolved in water to give a concentration of 2000 parts per million. A wetting agent, Triton X-100 , is added to this solution at the rate of 300 parts per million. Narcissus bulbs infested with the stem nematode (Ditylenchus dipsaci) are soaked in this bath for one-half to one hour followed by a drying period. Bulbs treated in this manner produce vigorous plants with dark-green . foliage while untreated bulbs produce weak and small plants with mottled or chlorotic foliage.

Example 9 Methyl l-(dimethylcarbamoyl) -N-(methylcarbamoyl-oxy) thioiformlmidate is slurried in water and used to treat rice seed infested with the rice white tip nematode (Aphelenchoides besseyl) at the rate of 5 to 10 grams of chemical to 1 kilogram of seed. Seed treated in this manner produce vigorous green plants while untreated seed produce plants with a condition known as "white tip".

Thiram fungicide is added to the seed treatment to control seedling blight.

Example 50 Methyl l-(dlmethylcarbamoyl) -N-(methylcarbamoyl-oxy) thio formlmidate is applied to a young citrus grove in Arizona infested with the citrus nematode (Tylenchulus semlpenetrans) by dissolving the chemical in the irrigation water. The equivalent of 4 to 5 kilograms per hectare of land is applied in 2.5 centimeters of irrigation water.

The young trees are protected from the injury of the citrus nematode, make rapid growth and begin producing a marketable fruit crop. A nearby grove not treated in this manner has poor growth, less vigorous trees and produces a light . crop of small fruit.

Example 51 methyl l-( dimethylcarbamoyl) -N-(methylcarbamoyloxy) - thio^formimldate 20$ methylthiolcarbamic acid, methyl ester 80$ The above formulation is diluted with mineral spirits and applied as a broadcast spray at the rate of 22 kilograms of formulation per hectare in a total volume of βθ liters per hectare to a field in Hawaii infested with the reniform nematode (Rotylenchulus reniformis) and the pin nematode (Paratylenchus minutus). The soil is then thoroughly mixed by disking. Pineapple plants grown in this field develop a deep extensive root system and make rapid growth. Plants in a nearly untreated field grow slowly due to a poor and shallow root system. -

Claims (8)

1. Compounds of the formula wherein ^ is alkyl of 1 through 4 carbon atoms or alkenyl of 3 through 4 carbon atoms; R2 is hydrogen, methoxy, alkyl of 1 through 4 carbon atoms, alkenyl of 3 carbon atoms or cycloalkyl of 3 through 5 carbon atoms} R^ is hydrogen, alkyl of 1 through 4 carbon atoms, or alkenyl of 3 "through, 4 carbon atoms ; R. is alkyl of 1 through 3 carbon atoms or allyl; and 4 R^ is hydrogen or aethyl; with the proviso that and ^ can be joined together a.nd form an alkylene of 2 through 6 carbon atoms, and with the further proviso that R„ and R_ rarer total more than 7 carbon atoms. 2 3

2. , A compound of Claim 1 wherein and ^ are both hydrogen.

3. A. compound of Claim 1 wherein ^ and R^ are both methyl.

4. · Methyl l-carbamoyl-N-(methylcarbamoyloxy)-thioformlmidate.

5. ethyl l-(dimethylcarbamoyl)-N-( methylcarbamoyloxy)thio-formimidate.

6. Methyl l-methylcarbamoyl-N-(methylcarbamoylox )-thioforrai-midate.

7. Methyl l-(diethylc rbamoyl)~K-(iiiethylcarbamoyloxy)-thio-foraiimida e.

8. A pesticidal composition comprising a major amount of a pesticidal diluent and a pesticidal amount of a compound of Claim 1. 9 /. A pesticidal composition comprising a major amount of a pesticidal diluent and a pesticidal amount of a compound of Claim 2. lO^. A' pesticidal composition comprising a major amount of a pesticidal diluent and a pesticidal amount of a compound of Claim 3. 11 H- A pesticidal composition comprising a major amount of a pesticidal diluent and a pesticidal amount of the compound of Claim 4. 12 A pesticidal composition comprising a major amount of a pesticidal diluent and a pesticidal amount of the compound of Claim 5. 13 JL/L. A method for controlling pests comprising applying to a locus to be protected a pest controlling amount of a compound of Claim 1. 14 M. A method for controlling pests comprising applying to a locus to be protected a pest controlling amount of a compound of Claim 2. 15 iV. A method for controlling pests comprising applying to a locus to be protected a pest controlling amount of a compound of Claim 3. 16 A method for controlling pests comprising applying to a locus to be protected a pest controlling amount of the compound of Claim 4. 17 y^. A method for controlling pests comprising applying to a locus ..-to be protected a pest controlling amount of the compound of Claim 5· 18 $. A method for controlling insects comprising applying to a locus to be protected an insect controlling amount of a compound of Claim 1. 19 7· A method for controlling insects comprising applying to a locus to be protected an insect controlling amount of a compound of Claim 2. 20 A method for controlling insects comprising applying to a locus to be protected an insect controlling amount of a compound of Claim 3. 21 1$. A method for controlling insects comprising applying to a locus to be protected an insect controlling amount of the compound of Claim 4. 22 P>. A method for controlling insects comprising applying to a locus to be protected an insect controlling amount of the compound of Claim 5. 23 A method for controlling insects, acarina and nematode pests comprising applying to pest infested soil a compound of Claim 1. 23 24 The method of Claim y in which the compound applied is methyl l-carbamoyl-N-(methylcarbamoyloxy) thio-formimidate. 23 25 Ι . The method of Claim[2 in which the compound applied is methyl l-(dimethylcarbamoyl) -N-(methylcarbamoyloxy) thioformlmidate . 263 . Α method for protecting plants from insects, acarina, and nematodes comprising applying to the plants a plant protectant amount of a compound of Claim 1. 26 279 The method of Claim fflt in which the compound applied is methyl 1-carbamoyl-N- (me hylcarbamoyloxy) thio-fo rmimidate. ' ' " . 26 ■ 28 9^. The method of Claim in which the compound applied is methyl l-(dimethylcarbamoyl) -N- (methylcarbamoyloxy) thioformimidate , 29 A method for protecting plants from insects, acarina, and nematodes comprising applying to the soil in which the plant is growing a plant protectant amount of a compound of Claim 1. , '; 29 30 β/. The method of Claim 9 in which the compound applied is methyl l-carbamoyl-N-(methylcarbamoyloxy) thio- ormimidate. .. . 29 31 The method of Claim fSfl/ in which the compound applied is methyl l-(dimethylcarbamoyl) -N- (methylcarbamoyloxy) thioformimidate. 32 /30. A method for controlling insect, acarina and nematode pests comprising applying to the pests a controlling amount of a compound of Claim 1. 32 33 ffl . The method of Claim ¾6 in which the compound applied is methyl l-carbamoyl-N-(methylcarbamoyloxy) thio-formimidate. 32 345¾f. The method of Claim fob in which the compound applied is methyl l-(dimethylcarbamoyl) -N-(methylcarbamoyl-